CN117603031A - Preparation method of beta-isophorone - Google Patents
Preparation method of beta-isophorone Download PDFInfo
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- CN117603031A CN117603031A CN202311563479.5A CN202311563479A CN117603031A CN 117603031 A CN117603031 A CN 117603031A CN 202311563479 A CN202311563479 A CN 202311563479A CN 117603031 A CN117603031 A CN 117603031A
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- Prior art keywords
- isophorone
- alpha
- preparation
- dimethyl
- beta
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- LKOKKQDYMZUSCG-UHFFFAOYSA-N 3,5,5-Trimethyl-3-cyclohexen-1-one Chemical compound CC1=CC(C)(C)CC(=O)C1 LKOKKQDYMZUSCG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- IITQJMYAYSNIMI-UHFFFAOYSA-N 3-Methyl-2-cyclohexen-1-one Chemical compound CC1=CC(=O)CCC1 IITQJMYAYSNIMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- 238000000066 reactive distillation Methods 0.000 claims description 4
- PIGJMFZYQUTSNI-UHFFFAOYSA-N 5,5-dimethyl-3-oxocyclohexene-1-carbaldehyde Chemical compound CC1(C)CC(=O)C=C(C=O)C1 PIGJMFZYQUTSNI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 5
- -1 0.002% Chemical compound 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000013793 astaxanthin Nutrition 0.000 description 1
- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 description 1
- 229940022405 astaxanthin Drugs 0.000 description 1
- 239000001168 astaxanthin Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of beta-isophorone. The product beta-isophorone is prepared by the reaction and rectification of a raw material alpha-isophorone composition. The method of the invention has the advantages of no addition of catalyst, environmental protection, high raw material conversion rate and easy industrialization.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of beta-isophorone.
Background
3, 5-trimethyl-3-cyclohexene-1-one is beta-isophorone for short, and is an important intermediate for synthesizing natural products such as vitamin E, carotenoid, astaxanthin and the like and spices.
U.S. patent No. 4005145a discloses a method for preparing a crude product of beta-isophorone by reaction and rectification by using adipic acid as a catalyst, and the purity of the obtained product can reach more than 91%. The method has the problems of more byproducts, low space-time yield, serious equipment corrosion and the like.
Chinese patent CN104649878B discloses a process for continuously synthesizing β -isophorone, comprising: taking alpha-isophorone as an initial raw material, taking a molecular sieve as a catalyst, carrying out isomerization reaction in a tower reactor by adopting a reactive distillation technology, collecting beta-isophorone at the top of the tower reactor, discharging heavy components in the tower reactor, and recycling to obtain alpha-isophorone for recycling; in the process, the molecular sieve catalyst is involved, the cost of raw materials is increased in the industrial amplification process, and the industrial production is inconvenient.
In summary, a green and environment-friendly preparation method of beta-isophorone is needed.
Disclosure of Invention
The invention aims to provide a preparation method of beta-isophorone, which does not need an additional catalyst in the preparation process and has the characteristics of environment friendliness and the like.
The technical scheme of the invention is as follows:
the preparation process of beta-isophorone with alpha-isophorone as material is reacted; no additional catalyst is needed;
wherein the raw material alpha-isophorone comprises the following components (the content of each substance is based on the mass of the alpha-isophorone):
0.0001-3wt% 3, 3-dimethyl-5-methylenecyclohex-1-one; and
0.0001-5wt% of 3-methyl-cyclohex-2-enone; and
0.0001-6wt% of 5, 5-dimethyl-3-oxocyclohex-1-eneformaldehyde; and
0.0001-2wt% 2, 6-trimethylcyclohexyl-1, 4-dione.
Preferably, the alpha-isophorone comprises the following components:
0.0001-1.5wt% 3, 3-dimethyl-5-methylenecyclohex-1-one, e.g., 0.005%, 0.1%, 0.5%, 1%, 1.2%, etc.; and
0.001-3wt% 3-methyl-cyclohex-2-enone, e.g., 0.002%, 0.01%, 0.1%, 0.5%, 1.2%, 1.5%, 2%, etc.; and
0.001-3.8wt% 5, 5-dimethyl-3-oxocyclohex-1-ene formaldehyde, e.g. 0.005%, 0.1%, 0.5%, 1%, 1.2%, 2%, 2.5%, etc.; and
iv.0.001 to 1wt% 2, 6-trimethylcyclohexyl-1, 4-dione, e.g. 0.002%, 0.01%, 0.05%, 0.1%, 0.5%, etc.
In a specific embodiment, the preparation method of the beta-isophorone of the present invention comprises: the raw material alpha-isophorone is added into a reaction rectifying tower from a tower kettle, and the temperature of the tower kettle is increased to react.
In the present invention, the theoretical plate number of the reactive distillation column is 3 to 100, preferably 25 to 60; the reflux ratio is 200:1 to 1:1, preferably 80:1 to 5:1.
In the present invention, the reaction is carried out at room temperature.
In the present invention, the reaction is warmed to 120℃to 300℃and preferably 150℃to 280℃and at a pressure of 0.05 to 5barA and preferably 0.2 to 3.2barA.
Compared with the prior art, the scheme provided by the invention has the following positive effects:
1) No catalyst is added, equipment corrosion is avoided, and the method is more beneficial to industrialized amplification and material selection.
2) The method is environment-friendly, does not introduce substances such as catalysts, auxiliary agents and the like, and reduces the generation amount of three wastes.
3) The utilization rate of raw materials is improved, the content of byproducts is reduced, and the production cost is reduced.
Detailed Description
The following examples will further illustrate the method provided by the present invention, but the invention is not limited to the examples listed and should include any other known modifications within the scope of the claimed invention.
The gas chromatograph is Agilent 7820A, and the gas chromatograph analysis conditions are: on-line measurement is carried out on the polysiloxane column HP-5 of Agilent gas chromatography, the temperature of a gasification chamber is 250 ℃, the temperature of a detector is 250 ℃, and the temperature of the column is programmed to rise: 50 ℃ for 1min;80 ℃ for 1min;10 ℃ per minute to 250 ℃ per minute, and the sample injection amount is 0.2 mu L.
Example 1
200.0kg of alpha-isophorone raw material (wherein 3, 3-dimethyl-5-methylenecyclohex-1-one content is 0.0012%, 3-methyl-cyclohex-2-enone content is 0.0020%, 5-dimethyl-3-oxocyclohex-1-eneformaldehyde content is 0.0015%, 2, 6-trimethylcyclohex-1, 4-dione content is 0.0014%) is added into a stainless steel rectifying tower kettle with 25 theoretical plates at normal temperature, the pressure at the top of the rectifying tower is maintained at 2.6barA, then the temperature of the tower kettle is slowly raised to boiling, the kettle temperature is 263-264 ℃, after reflux is established at the top of the tower, the reflux quantity at the top of the tower is slowly raised to 80.0kg/h, the total reflux is carried out for about 1h, the material was withdrawn from the top of the column at a rate of 4.0kg/h while the column bottom was fed with an alpha-isophorone raw material (3, 3-dimethyl-5-methylenecyclohex-1-one content 0.0012%, 3-methyl-cyclohex-2-enone content 0.0020%, 5-dimethyl-3-oxocyclohex-1-eneformaldehyde content 0.0015%, 2, 6-trimethylcyclohex-1, 4-dione content 0.0014%) at a feed rate of 4.0kg/h, the column bottom reaction liquid volume was maintained constant throughout the rectification process, the column bottom temperature was maintained at 263-264 ℃ (slightly elevated temperature over time) after 720 hours of stable operation), and the gas phase analysis was performed on the withdrawn material from the column top, wherein the product beta-isophorone content was 99.6%.
Example 2
Adding 260.0kg of alpha-isophorone raw material (3, 3-dimethyl-5-methylene cyclohex-1-one content 0.59%, 3-methyl-cyclohex-2-enone content 2.70%, 5-dimethyl-3-oxo cyclohex-1-ene formaldehyde content 0.33%, 2, 6-trimethyl cyclohex-1, 4-dione content 0.89%) into a stainless steel rectifying tower kettle with 60 theoretical plates at normal temperature, maintaining the top pressure of the reaction rectifying tower at 0.25barA, then slowly heating the tower kettle to boiling, keeping the kettle temperature at 164-165 ℃, slowly increasing the reflux amount of the tower top to 100.0kg/h after the reflux is established at the tower top, completely refluxing for about 1h, the material was withdrawn from the top of the column at a rate of 1.2kg/h while the reaction liquid volume of the column was maintained constant throughout the rectification, the temperature of the column was maintained at 164 to 165℃after 720 hours of steady operation (slightly elevated temperature over time), and the gas phase analysis was performed on the withdrawn material from the top of the column, with the product β -isophorone content of 95.8%.
Example 3
220.0kg of alpha-isophorone raw material (3, 3-dimethyl-5-methylenecyclohex-1-one content 1.03%, 3-methyl-cyclohex-2-enone content 0.94%, 5-dimethyl-3-oxocyclohex-1-ene formaldehyde content 1.77%, 2, 6-trimethylcyclohex-1, 4-dione content 0.26%) is added into the bottom of a stainless steel rectifying tower with 45 theoretical plates at normal temperature, the top pressure of the rectifying tower is maintained at 1.5barA, then the bottom is slowly heated to boiling, the temperature of the bottom is 239-240 ℃, after reflux is established at the top of the tower, the reflux amount of the top of the tower is slowly increased to 40.0kg/h, the total reflux is performed for about 1h, the material was withdrawn from the top of the column at a rate of 8.0kg/h while the reaction liquid volume of the column was maintained constant throughout the rectification, the temperature of the column was maintained at 239-240℃after 720 hours of steady operation (slightly elevated temperature over time), and the gas phase analysis was performed on the withdrawn material from the top of the column, with the product β -isophorone content of 95.1%.
Comparative example 1
200.0kg of pure alpha-isophorone is added into a stainless steel rectifying tower kettle with 25 theoretical plates at normal temperature, the top pressure of the reactive rectifying tower is maintained at 2.6barA, then the tower kettle is slowly heated to boiling, the kettle temperature is 263-264 ℃, after reflux is established at the tower top, the reflux amount of the tower top is slowly increased to 80.0kg/h, after total reflux is about 1h, the material is extracted from the tower top at the rate of 4.0kg/h, meanwhile, the pure alpha-isophorone is fed into the tower kettle, the feeding rate is 4.0kg/h, the reaction liquid volume of the tower kettle is maintained constant in the whole rectifying process, the kettle temperature is maintained at 263-264 ℃ (slightly increased along with the time after the stable operation is carried out for 720 h), and the gas phase analysis is carried out on the extracted material at the tower top, wherein the content of beta-isophorone is 9.4%.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (7)
1. A preparation method of beta-isophorone is characterized in that alpha-isophorone is used as a raw material, no catalyst is added in the preparation process,
the raw material alpha-isophorone comprises the following components, wherein the content of each substance is based on the mass of the alpha-isophorone:
0.0001-3wt% 3, 3-dimethyl-5-methylenecyclohex-1-one; and
0.0001-5wt% of 3-methyl-cyclohex-2-enone; and
0.0001-6wt% of 5, 5-dimethyl-3-oxocyclohex-1-eneformaldehyde; and
0.0001-2wt% 2, 6-trimethylcyclohexyl-1, 4-dione.
2. The preparation method according to claim 1, wherein the alpha-isophorone comprises the following components:
0.0001-1.5wt% 3, 3-dimethyl-5-methylenecyclohex-1-one; and
0.001-3wt% of 3-methyl-cyclohex-2-enone; and
0.001-3.8wt% of 5, 5-dimethyl-3-oxocyclohex-1-eneformaldehyde; and
0.001-1wt% of 2, 6-trimethylcyclohexyl-1, 4-dione.
3. The preparation method according to claim 1, wherein the raw material alpha-isophorone is added into the reaction rectifying tower from a tower bottom, and the tower bottom is heated for reaction.
4. The production method according to claim 1, wherein the theoretical plate number of the reactive distillation column is 3 to 100; the reflux ratio is 200:1-1:1.
5. The production method according to claim 1, wherein the theoretical plate number of the reactive distillation column is 25 to 60; the reflux ratio is 80:1-5:1.
6. The process according to any one of claims 1 to 5, wherein the reaction temperature is 120℃to 300℃and the pressure is 0.05 to 5barA.
7. The process according to any one of claims 1 to 5, wherein the reaction temperature is 150℃to 280℃and the pressure is 0.2 to 3.2barA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311563479.5A CN117603031A (en) | 2023-11-22 | 2023-11-22 | Preparation method of beta-isophorone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311563479.5A CN117603031A (en) | 2023-11-22 | 2023-11-22 | Preparation method of beta-isophorone |
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| Publication Number | Publication Date |
|---|---|
| CN117603031A true CN117603031A (en) | 2024-02-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311563479.5A Pending CN117603031A (en) | 2023-11-22 | 2023-11-22 | Preparation method of beta-isophorone |
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| Country | Link |
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| CN (1) | CN117603031A (en) |
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2023
- 2023-11-22 CN CN202311563479.5A patent/CN117603031A/en active Pending
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